CN1607685A - Composition for preparing organic insulator - Google Patents
Composition for preparing organic insulatorDownload PDFInfo
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- CN1607685A CN1607685ACNA2004100881621ACN200410088162ACN1607685ACN 1607685 ACN1607685 ACN 1607685ACN A2004100881621 ACNA2004100881621 ACN A2004100881621ACN 200410088162 ACN200410088162 ACN 200410088162ACN 1607685 ACN1607685 ACN 1607685A
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Abstract
Translated fromChinese
Description
Background of the present invention
The priority that this non-provisional application requires is at the korean patent application No.2003-71775 of 2003.10.15 application by 35U.S.C. § 119 (a) regulation, lists for reference here in the lump.
Technical field
The present invention relates generally to be used to make the composition of organic insulator.More particularly, the present invention relates to be used to make the composition of organic insulator, and the organic insulator that adopts said composition to make.Said composition contains (i) hybrid inorganic-organic materials; (ii) at least a kind of organo-metallic compound and/or organic polymer; And (iii) a kind of dissolved constituent (i) and solvent (ii) of being used for.
The explanation of correlation technique
Thin-film transistor (below be called ' TFT ') uses in the display unit of being everlasting, and is made of the silicon insulating film and the metal electrode of Si semiconductor film, oxidation.At present, be used for semi-conducting material organic tft oneself through the exploitation (U.S. Patent No. 5,347,114).Because it has good properties, oneself studies this material all over the world.Specifically, organic tft is flexible, and is convenient to make, and has quickened the application in their field of display on the scene.
Since polyacetylene, a kind of exploitation of organic polymer of the conjugation with characteristic of semiconductor, to the research of organic polymer semiconductor material just in mushroom development.This material is used widely in different fields as the base material of novel electron device, for example, and functional electronics device and Optical devices.This is because when using in organic semiconductor, organic polymer presents lot of advantages: they can adopt various synthetic route and synthesize at low cost; They can easily make fiber or film; And they present good flexible and good conductivity.
A kind of as in a lot of devices that use the organic conductive polymer to make since 1980, studies as active membrane to being characterized as the organic tft that contains organic polymer.In recent years, this organic tft had been carried out broad research in the whole world.This organic tft has the structure that is similar to Si-TFT commonly used, so but its difference at a kind of organic polymer that uses as semi-conducting material that replaces silicon.In the method for making organic tft, the film of semiconductor layer is under atmospheric pressure to make by print process.This method with use plasma method opposite, it is by chemical vapour desposition (CVD), this method is loaded down with trivial details but come down to be used for the formation of silicon thin film.Yet, concerning organic tft, can use a kind of roll-in method that adopts the continuous rolling of plastic basis material, so that can low-costly make transistor.
Usually, in charge carrier mobility, organic tft is parity with or superiority over amorphous silicon TFT, but their driving and threshold voltage are very high.Adopt amorphous silicon and pentacene (pentacence), charge carrier mobility is 0.6cm2/ V-second (N.Jackson, 54ThAnnual Device Research Conference Digest1996), but have some problems, driving voltage is greater than 100V, and subthreshold voltage is 50 times of amorphous silicon.
For controlling and driving voltage and reduction threshold voltage, at adopting high k insulator to carry out very small amount of research, not only in silicon TFT field, and in organosilicon TFT field (U.S. Patent No. 5,981,970, Science, Vol.283, p822～824, Organic Electronics 3,65～72).For example, ferroelectric insulating material, for example BaxSr1-xTiO3(BST), Ta2O5, Y2O3Or TiO2, and have dielectric than greater than 15 inorganic insulating material, for example PbZrxTi1-xO3(PZT), Bi4Ti3O12, BaMgF4, SrBi2(Ta1-xNbx)2O9, Ba (Zr1-xTix) O3(BZT), BaTiO3Or SrTiO3Existing report (U.S. Patent No. 5,946,551).Adopt the device of these materials both can adopt sedimentation (CVD, sputtering method or ALD method) also can adopt sol-gel process to be coated with.The charge carrier mobility of existing report device is less than 0.6cm2/ V-second and driving voltage are less than-5V.Yet with regard to various matrixes, because require high temperature (200～400 ℃) in most of manufacture method, this has limited use.Also have, it is difficult to adopt the print process manufacturing installation.At present, contain the organic insulating film of polyimides, BCB (benzocyclobutene), photosensitive acryloyl group etc., (U.S. Patent No. 6,232,157) can not adapt with the character of inorganic insulator.
At present, on various drive units, use organic tft to do a lot of researchs.Yet in order to realize the actual use of organic tft, not only LCD (LCD) but also contain the flexible display of organic electroluminescent device requires the charge carrier migration rate to be higher than 10cm2/ V-second.In addition,, require in manufacture method, on plastic basis material, be coated with dielectric film by all print method or full spin-coating method for easy and cost reduce.Many researchs have been carried out at organic insulation private savings with simple manufacturing method and improved charge carrier migration rate.Focus provides a kind of advantage that forms organic active layer, compares with inorganic insulating membrane, and the granular size of organic active layer is increased.Usually, the dielectric ratio that these organic insulating films show is 3～4, and it requires the high driving voltage of 30～50V and the high threshold voltage of 15～20V.
In order to increase the dielectric ratio, the someone attempts the ferroelectric ceramic particle (U.S. Patent No. 6,586,791) of dispersing nanometer level size in insulating polymer.But also there is some problem in this method.Ceramic particle influences the formation of organic active layer, thereby reduces charge carrier mobility or increase leakage current.This just needs to use the other dielectric film with good dielectricity.Therefore, in the prior art, must develop have high dielectric than and good insulating properties and organic tft that increase semiconductor demonstration property.
The present invention's summary
Carry out the present invention in view of the above problems, the purpose of this invention is to provide a kind of composition that is used to make organic insulator, this organic insulator presents low threshold value and driving voltage and high charge carrier mobility.
Another object of the present invention provides a kind of method that adopts above-mentioned composition to make organic insulator.
Another purpose of the present invention provides a kind of by said method manufacturing organic insulator.
A further object of the present invention provides a kind of organic tft of making from above-mentioned composition.
According to purpose of the present invention, a kind of composition that is used to make organic insulator is provided, said composition contains (i) at least a kind of hybrid inorganic-organic materials; (ii) at least a kind of organo-metallic compound and/or organic polymer; (iii) at least a kind is used for dissolved constituent (i) and solvent (ii).
According to another object of the present invention, a kind of method that is used to make organic insulator is provided, this method comprises: use the above-mentioned composition coated substrate to form dielectric film; And curing dielectric film.
According to another purpose of the present invention, provide a kind of organic insulator made from said method.
According to a further object of the present invention, a kind of OTFT is provided, this transistor contains: matrix; Gate electrode; Dielectric film; Organic active layer; Source-drain electrode, wherein, dielectric film is above-mentioned organic insulator.
Description of drawings
Above-mentioned and other purpose of the present invention, characteristic and other advantages, following detailed description in conjunction with the drawings will more be expressly understood.Wherein:
Fig. 1 is the simple sectional view of the thin-film transistor used always;
Fig. 2 is the organic tft drive characteristic figure thatexplanation embodiment 5 makes;
Fig. 3 is the organic tft drive characteristic figure thatexplanation embodiment 7 makes.
Detailed description of the present invention
Below, the present invention is carried out in more detail explanation.
Be used for the composition of organic insulator of the present invention, comprise: (i) at least a kind of hybrid inorganic-organic materials; (ii) at least a kind of organo-metallic compound and/or organic polymer; (iii) at least a kind is used for dissolving the solvent of above-mentioned 2 kinds of components.
In the present invention, hybrid inorganic-organic materials can be organic silane compound or have in the presence of acid or the base catalyst, the hybrid inorganic-organic polymer that hydrolysis and the polycondensation by organic silane compound forms. Preferably, hybrid inorganic-organic materials can be withformula formula
SiX1X2X3X4
R1SiX1X2X3
R1R2SiX1X2
Informula 1～3, R1And R2Each represents hydrogen atom, C independently1-10Alkyl, C3-10Cycloalkyl, C6-15Aryl, C2-30Acryloyl group or contain alkyl, cycloalkyl or the aryl of epoxy radicals; And,
X1, X2, X3And X4Each represents halogen atom or C independently1-5Alkoxyl.
As the acid catalyst that is used to make the hybrid inorganic-organic polymer, can enumerate hydrochloric acid, nitric acid, benzene sulfonic acid, oxalic acid, formic acid etc.As base catalyst, can enumerate potassium hydroxide, NaOH, triethylamine, sodium acid carbonate, pyridine etc.The catalyst that uses in hydrolysis and polycondensation is preferably 0.000001: 1～10: 1 to the mol ratio of monomer total amount.
The water that uses when making the hybrid inorganic-organic polymer is preferably 1: 1～1000: 1 to the mol ratio of monomer total amount.
The unrestricted example of the organic solvent that uses when making the hybrid inorganic-organic polymer comprises for example hexane of aliphatic solvent; Aromatic hydrocarbon solvent is methyl phenyl ethers anisole, 1,3 for example, 5-trimethylbenzene and dimethylbenzene; Ketones solvent is methyl iso-butyl ketone (MIBK), 1-Methyl-2-Pyrrolidone, cyclohexanone and acetone for example; Ether solvent is oxolane and isopropyl ether for example; The acetate esters solvent is ethyl acetate, butyl acetate and propylene glycol methyl ether acetate for example; Alcohols solvent is isopropyl alcohol and butanols for example; Amide solvent is dimethylacetylamide and dimethyl formamide for example; The silicon kind solvent; And their mixture.
According to the present invention, hydrolysis and polycondensation were preferably carried out 0.1～100 hour under 0～200 ℃ of temperature.
Therefore, the Mw of the hybrid polymer of manufacturing is preferably 3,000～300,000 scope.
According to the present invention, organo-metallic compound is meant the compound with good insulation performance and high dielectric ratio, and it comprises having dielectric than 4 or bigger metal oxide.The unrestricted example of organo-metallic compound, comprise for example n-butanol titanium (IV) of titanium compound, tert-butyl alcohol titanium (IV), titanium ethanolate (IV), 2-Ethylhexyl Alcohol titanium (IV), isopropyl titanate (IV), (two-isopropoxy) two (pentanedione acid esters) titaniums (IV), two (pentanedione acid esters) titanium oxide (IV), trichlorine three (oxolane) titanium (III), three (2,2,6,6-tetramethyl-3,5-pimelic acid ester group) titanium (III), (trimethyl) pentamethyl cyclopentadienyltitanium (IV), pentamethyl cyclopentadienyl group titanium trichloride (IV), pentamethyl cyclopentadienyl group trimethoxy titanium (IV), two (cyclohexyl sulfydryl) titaniums (IV) of tetrachloro, two (oxolane) titaniums (IV) of tetrachloro, tetrachloro diamines titanium (IV), four (diethylamino) titanium (IV), four (dimethylamino) titanium (IV), two (tert-butyl group cyclopentadienyl group) titanium chloride, two (cyclopentadienyl group) dicarbapentaborane titanium (II), two (cyclopentadienyl group) titanium chloride, two (ethyl cyclopentadienyl group) titanium chloride, two (pentamethyl cyclopentadienyl group) titanium chloride, two (isopropyl cyclopentadienyl group) titanium chloride, three (2,2,6,6-tetramethyl-3,5-pimelic acid ester group) oxygen titanium (IV), three isopropoxy chlorine titaniums, the cyclopentadienyl group titanium trichloride, dichloro two (2,2,6,6-tetramethyl-3,5-pimelic acid ester group) titanium (IV), two (tert-butyl group cyclopentadienyl group) titaniums (IV) of dimethyl, with two (isopropoxy) two (2,2,6,6-tetramethyl-3,5-pimelic acid ester group) titanium (IV); The zirconium compounds is zirconium-n-butylate (IV), zirconium tert-butoxide (IV), ethanol zirconium (IV), zirconium iso-propoxide (IV), zirconium-n-propylate (IV), zirconium acetylacetonate (IV), hexafluoro zirconium acetylacetonate (IV), trifluoroacetyl group pyruvic acid zirconium (IV), four (diethylamino) zirconium, four (dimethylamino) zirconium, four (2 for example, 2,6,6-tetramethyl-3,5-pimelic acid ester group) zirconium (IV) and zirconium sulfate (IV) tetrahydrate; The hafnium compounds is n-butanol hafnium (IV), tert-butyl alcohol hafnium (IV), ethanol hafnium (IV), isopropyl alcohol hafnium (IV), isopropyl alcohol one isopropyl acid hafnium (IV), pentanedione acid hafnium (IV), four (dimethylamino) hafnium for example; And; the aluminium compounds is Tributyl aluminate, tert-butyl alcohol aluminium (IV), aluminium secondary butylate, aluminium ethylate, aluminium isopropoxide, pentanedione acid aluminium, hexafluoro pentanedione acid aluminium, trifluoroacetyl group pyruvic acid aluminium and three (2,2,6 for example; 6-tetramethyl-3,5-pimelic acid ester group) aluminium.
The ratio of the organo-metallic compound that uses in the present composition based on the hybrid inorganic-organic materials of 100 weight portions, is preferably 1～300 weight portion, more preferably 5～100 weight portions.When this ratio during greater than 300 weight portions, produce excessive leakage current, cause IOn/ IOffRatio and charge carrier mobility worsen.When this ratio during, be difficult to form film, and charge carrier mobility descends obviously less than 1 weight portion.
Above-mentioned organic polymer comprises many polymer that present insulating property (properties).The limiting examples of insulating properties organic polymer comprises polyester, Merlon, polyvinyl alcohol, polyvinyl butyral, polyacetals, poly-virtueization thing, polyamide, polyamidoimide, Polyetherimide, polyphenylene ether, polyphenylene sulphur, polyether sulfone, polyether-ketone, polyphtalamide, the polyethers nitrile, polyether sulfone, polybenzimidazoles, poly-carbonization imidodicarbonic diamide, polysiloxanes, polymethyl methacrylate, PMAm, nitrile rubber, acrylic rubber, polytetrafluoroethylene, epoxy resin, phenol resin, melamine resin, urea resin, polybutene, polypenthylene, poly-(ethene-copolymerization-propylene), poly-(ethene-copolymerization-butadiene), polybutadiene, polyisoprene, poly-(ethene-copolymerization-propylene diene), butyl rubber, polymethylpentene, polystyrene, poly-(styrene-copolymerization-butadiene), hydrogenation gathers (styrene-copolymerization-butadiene), hydrogenated polyisoprene and hydrogenated butadiene polymer.
The organic polymer ratio of using in the composition of the present invention is preferably 0.01～50 weight portion based on the hybrid inorganic-organic materials of 100 weight portions, more preferably 0.1～25 weight portion.When this ratio greater than 50 the time, the character of device obviously worsens.When this ratio is lower than 0.01 weight portion, be difficult to form film by spin-coating method.
In the present invention, the electrical properties of organic insulator, for example ratio that dielectric constant, leakage current etc. can be by changing hybrid inorganic-organic materials and the organo-metallic compound in the composition and/or organic polymer are controlled.
The limiting examples of the organic solvent that uses in the present composition comprises for example hexane of aliphatic solvent; Aromatic hydrocarbon solvent is methyl phenyl ethers anisole, 1,3 for example, 5-trimethylbenzene and dimethylbenzene; Ketones solvent is methyl iso-butyl ketone (MIBK), 1-Methyl-2-Pyrrolidone, cyclohexanone and acetone for example; Ether solvent is oxolane and isopropyl ether for example; The acetate esters solvent is ethyl acetate, butyl acetate and propylene glycol methyl ether acetate for example; Alcohols solvent is isopropyl alcohol and butanols for example; Amide solvent is dimethylacetylamide and dimethyl formamide for example; The silicon kind solvent; And their mixture.
The consumption of organic solvent should be enough to make solid constituent, comprises hybrid inorganic-organic materials and organo-metallic compound, is coated on substrate surface equably.In this respect, the organic solvent content in the composition is 20～99.9 weight %, preferred 70～95 weight %.If the concentration of organic solvent is less than 20 weight %, the solid constituent part is not dissolved.On the other hand, if the content of organic solvent greater than 99.9 weight %, final film can be thinned to 1000 or lower.
In the present invention, provide a kind of method of making organic insulator, this method comprises: the film of coating above-mentioned composition and curing coating on matrix.The limiting examples of coating process comprises among the present invention: spin-coating method, dip coating, print process, spraying process and rolling method, and spin-coating method is most preferred.Curing is to add hot basal body 0.5～2 hour and carry out under 70～150 ℃ of temperature.
The organic insulator of making shows good insulating properties according to the method described above.When it uses TFF, can obtain high charge carrier mobility, low driving and threshold voltage and good IOn/ IOffRatio.Especially, adopt wet method for example print process or spin-coating method can make dielectric film, thereby the properties of the organic tft of manufacturing can be equal to mutually with the TFT of the inorganic insulating membrane that uses the CVD manufactured.
In addition, the invention provides a kind of organic tft that contains above-mentioned organic insulator as insulating barrier.Fig. 1 illustrates the sketch of general OTFT (TFT).This TFT comprises:matrix 1;Dielectric film 2; Organicactive film 3;Gate electrode 4;Source electrode 5 and drain electrode 6.But the present invention can be used for the TFT of each refreshing type and is not limited to TFT shown in Figure 1.
Preferably make base material with plastics, glass, silicon etc.
In organic tft of the present invention, organic active layer can with any oneself know that organic semiconducting materials comprises that any material of conducting polymer makes.Preferably organic active layer is by following made: pentacene, CuPc, polythiophene, polyaniline, polyacetylene, polypyrrole, polyphenylene vinylene or derivatives thereof, but be not limited thereto.
Gate electrode and source electrode/drain electrode are to be made by gold (Au), silver (Ag), aluminium (Al), nickel (Ni) and indium tin oxide (ITO), but are not limited thereto.
Below, illustrate in greater detail the present invention with reference to the following example.Yet these embodiment only are used for explanation and do not limit the scope of the invention.
The polymer that adopts methacryloxypropyl trimethoxy silane (below be called MAPTMS) is as hybrid inorganic-organic materials.The MAPTMS of 80.531mmol (20g) is put into flask, then, the hydrochloric acid solution 3.5ml in the deionized water (0.001021 mol hydrochloric acid/1ml water) is imported in the flask.This mixture reacted under room temperature 30 minutes, then, for inhibitory reaction, added oxolane 100ml and diethyl ether 100ml in mixture.Reactant mixture is transferred to separatory funnel and washes withwater 3 times.After the washing, make the volatile materials evaporation under the decompression, produce the liquid MAPTMS polymer of colourless thickness.This polymer is dissolved in 15ml acetone, and filters this solution, so that remove tiny powder and impurity with the filter of 0.2 μ m size.Then, separate liquid phase, under reduced pressure remove volatile material, obtain 13g colourless liquid polymer.
MAPTMS polymer and four titanium butoxide (Ti (OC4H9)4) mixture (70: 30 weight ratios) be dissolved in butanols, concentration is 10 weight %.With spin-coating method this solution coat on glass basis, to form the film of thick 7000 , then, this film in 70 ℃ ofhot curings 1 hour, was solidified 30 minutes in 150 ℃, to produce dielectric film again.In addition, deposit the pentacene of 700 by OMBD (OMBD).At this moment, 2 * 10-6Deposit under the condition of torr vacuum pressure, 80 ℃ of substrate temperatures and deposition rate 0.3A/ second.Then, with the shadow mask with passage length 100 μ m andchannel width 1 μ m, formation source-drain electrode on the pentacene active membrane obtains final organic tft.The charge carrier mobility of the organic tft of manufacturing, threshold voltage and LOn/ LOffThan measuring, and be shown in table 1 according to following explanation.
(1) charge carrier mobility, threshold voltage
The device charge carrier mobility, by following formula (4) by (ISD)1/2And VGThe slope of graph of a relation calculates, wherein, according to the mapping of the current equation of following zone of saturation (1) and (2), and by under establish an equation (3) calculate Dou and lead:
In above-mentioned equation (1)～(4), ISD: source-leakage current; μ or μFET: charge carrier mobility; C0: the electric capacity of insulating barrier; W: channel width; L: passage length; VG: gate voltage; And, VT: threshold voltage.
Threshold voltage (VT) from VG(I is represented in the axle crosscutSD)1/2And VGThe crosspoint of the extended line of the straight line portion of graph of a relation obtains.When the absolute value approximate zero of threshold voltage, power consumption descends.
(2) IOn/ IOffRatio
IOn/ IOffThan the maximum current when starting and the minimum current ratio when closing measure, and with under establish an equation (5) represent:
In above-mentioned equation (5), IOn: maximum current; IOff: the leakage current of closed condition; μ: charge carrier migration rate; σ: active layer conductance; Q: electric charge; NA: charge density; T: thickness of insulating layer; C0: the electric capacity of insulating barrier; VD: drain voltage.
As by shown in this equation, dielectric constant thickness bigger and dielectric film is littler, resulting IOn/ IOffBigger than.Therefore, the kind of dielectric film and thickness are the I that determinesOn/ IOffThe deciding factor of ratio.
Table 1
| MAPTMS polymer (g) | Ti(OC4H9)4????(g) | ????Ion/IoffRatio | Charge carrier mobility (cm2/V·s) | Threshold voltage (V) | |
| ????0.7 | ????0.3 | ????1000 | ????15 | ????-4 |
As shown in table 1, organic tft presents the charge carrier mobility greater than 10, and it is maximum value in known insulating material.In addition, threshold voltage causes the low voltage drive characteristic less than-5V.
The butanol solution for preparing the polyvinyl butyrate (below be called PVB) of 7 weight %.With mixed MAPTMS polymer shown in the table 2 and PVB solution, and make dielectric film with this mixture.Forming the method for dielectric film and the method for manufacturing organic tft all carries out according to method same among the embodiment 1.In addition, the character of resulting organic tft is measured according to method same among theembodiment 1.
Table 2
| PVB solution (g) | MAPTMS polymer (g) | ??Ion/IoffRatio | Charge carrier mobility (cm2/V·s) | Threshold voltage (V) | |
| Embodiment 2-1 | ????0.75 | ????0.25 | ????300,00 | ????8 | ??-11.45 |
| Embodiment 2-2 | ????0.5 | ????0.5 | ????200,00 | ????8 | ???-8.7 |
As shown in table 2, organic tft presents greater than 105IOn/ IOffRatio is greater than 8cm2The charge carrier mobility of/Vs, the transistor characteristic that corresponding demonstration is good.
The butanol solution for preparing the PVB of 7 weight %.Press the mixed PVB solution shown in the table 3, MAPTMS polymer and butyl titanate, and this mixture is spun onto the thick film of 2000 on aluminium base, then, this film was solidified 1 hour and solidified 30 minutes in 150 ℃ in 70 ℃, to make dielectric film.Be that deposition of aluminum film is to form the capacitor arrangement of M-I-M (metal-insulator-metal type) on this dielectric film.Adopt it, in the capacitor C of 100kHz measurement unit area0From the dielectric ratio that records, press following formula (6) and measure dielectric constant:
C0＝εε0(A/d)????????????????(6)
Wherein, C0Be dielectric electric capacity; ε and ε0Be respectively the dielectric constant of dielectric material and vacuum; A is the area of device; And d is the thickness of dielectric material.
Table 3
| Solution (g) | Ti(OC4H9)4(g) | MAPTMS polymer (g) | Dielectric constant κ | |
| Embodiment 3-1 | ??0.1g | ????0.25g | ????0.25g | ????5.82 |
| Embodiment 3-2 | ??0.1g | ????0.25g | ????0.75g | ????5.1 |
| Embodiment 3-3 | ??0.1g | ????0.75g | ????0.25g | ????7.1 |
| Embodiment 3-4 | ??0.1g | ????0.75g | ????0.75g | ????6.2 |
The butanol solution for preparing the PVB of 7 weight %.Press the mixed PVB solution shown in the table 4, MAPTMS polymer and butyl titanate, and use this mixture to make dielectric film.Forming the method for dielectric film and the method for manufacturing organic tft carries out according to method same among the embodiment 1.In addition, the character of resulting organic tft is measured according to method same among theembodiment 1.
Table 4
| PVB solution (g) | ??Ti(OC4H9)4????(g) | MAPTMS polymer (g) | ??Ion/IoffRatio | Charge carrier mobility (cm2/V·s) | Threshold voltage (V) | |
| Embodiment 4-1 | ????0.1 | ????0.25 | ????0.25 | ????395 | ????8.26 | ????-2.2 |
| Embodiment 4-2 | ????0.1 | ????0.25 | ????0.75 | ????67000 | ????30 | ????-3.1 |
| Embodiment 4-3 | ????0.1 | ????0.75 | ????0.25 | ????12 | ????0.65 | ????-0.3117 |
| Embodiment 4-4 | ????0.1 | ????0.75 | ????0.75 | ????1260 | ????6.61 | ????-1 |
| Embodiment 4-5 | ????0.3 | ????0.5 | ????0.5 | ????1990 | ????4.31 | ????-2.3 |
| Embodiment 4-6 | ????0.5 | ????0.25 | ????0.25 | ????2120 | ????3.25 | ????-2.53 |
| Embodiment 4-7 | ????0.5 | ????0.25 | ????0.75 | ????70400 | ????24.5 | ????-5.72 |
| Embodiment 4-8 | ????0.5 | ????0.75 | ????0.25 | ????16.2 | ????1.48 | ????-1.37 |
| Embodiment 4-9 | ????0.5 | ????0.75 | ????0.75 | ????1180 | ????3.77 | ????-0.485 |
As can be seen, the increase of organic titanium causes charge carrier mobility and I in table 4On/ IOffThe reduction of ratio, and threshold voltage also descends.In addition, the increase of also finding out the MAPTMS polymer causes charge carrier migration rate and IOn/ IOffThe increase of ratio, charge carrier mobility are increased to 100 times, IOn/ IOffThan being increased to 10000 times.
In the mixture of PVB solution (7 weight %) 0.15g and butyl titanate 0.35g, sneak into 0.1g, 0.25g, 0.5g and 0.75g MAPTMS polymer respectively, and make dielectric film with these mixtures.Forming the method for dielectric film and the method for manufacturing organic tft carries out according to method same among the embodiment 1.The drive characteristic of resulting TFT is shown in Fig. 2.In Fig. 2, along with the increase of hybrid inorganic-organic materials amount, leakage current reduces, and electric current that passes through (on-current) and charge carrier mobility increase.Threshold voltage is lower than-5V, and it is lower than organic insulator commonly used.
In the ratio shown in the table 5, mix MAPTMS polymer, epoxy resin and butyl titanate, and, make solution toward wherein adding butanols.According to the same mode ofembodiment 1, with spin-coating method this solution coat on base material, make dielectric film, then, it is solidified according to the condition shown in the table 5.According to the same manner ofembodiment 1, make organic tft, the character of organic tft is measured according to the same manner ofembodiment 1.
Table 5
| Epoxy resin (g) | ?Ti(OC4H9)4????(g) | MAPTMS polymer (g) | Condition of cure | ???κ | ?Ion/IoffRatio | Charge carrier mobility (cm2/V·s) | Threshold voltage (V) | |
| Embodiment 6-1 | ????0.05 | ????0.45 | ????0.25 | (150 ℃) are heating and curing | ??5.75 | ???100 | ????0.2 | ???-5 |
| Embodiment 6-2 | ????0.05 | ????0.45 | ????0.5 | (150 ℃) are heating and curing | ??5.53 | ???1000 | ????6 | ???-3 |
| Embodiment 6-3 | ????0.05 | ????0.45 | ????0.75 | (150 ℃) are heating and curing | ??5.76 | ???9600 | ????25 | ???-4.2 |
| Embodiment 6-4 | ????0.05 | ????0.45 | ????0.25 | UV curing (600W, 10min) | ??5.9 | ???31 | ????0.1 | ????0.1 |
| Embodiment 6-5 | ????0.05 | ????0.45 | ????0.5 | UV curing (600W, 10min) | ??5.57 | ???121000 | ????30 | ???-6.5 |
| Embodiment 6-6 | ????0.05 | ????0.45 | ????0.75 | UV curing (600W, 10min) | ??5.65 | ???720000 | ????47 | ???-9 |
In table 5, can see use epoxy resin, be directed at and similarly drive when using PVB character.Find that also electrical properties not only changes along with the amount of used hybrid inorganic-organic materials but also along with curing.Under the situation of embodiment 6-6, the charge carrier mobility of this device and IOn/ IOffThan showing high value.
In the mixture of PVB solution (7 weight %) 0.15g and butyl titanate 0.35g, add 0.75gMAPTMS, and this mixture is dissolved in butanols to make 10 weight % solution.According to this solution of method spin coating same among the embodiment 1.Carry out the manufacturing of organic tft according to method same among theembodiment 1, the character of the organic tft that measures according to method same among the embodiment.From Fig. 3, the I of calculatingOn/ IOffRatio is about 104And the charge carrier migration rate is about 3～5cm2/ Vs.At this moment, IOn/ IOffWhen the charge carrier migration rate is reduced to a certain degree, but sees prepared organic TFT, compares with existing organic insulator, has good properties.
For illustrative purposes, although the invention discloses embodiment preferred,, can carry out various improvement, interpolation and displacement not departing from scope and spirit of the present invention disclosed in the accompanying claims.
Claims (15)
1. composition that is used to make organic insulator, it comprises: (i) at least a kind of hybrid inorganic-organic materials; (ii) at least a kind of organo-metallic compound and/or organic polymer; (iii) at least a kind is used to dissolve said components (i) and solvent (ii).
2. according to the composition of claim 1, wherein, hybrid inorganic-organic materials is organic silane compound or having in the presence of acid or the base catalyst, the polymer that hydrolysis and the polycondensation by organic silane compound forms.
3. according to the composition of claim 2, wherein, organic silane compound is selected from the compound of representing with following formula 1～3:
Formula 1
SiX1X2X3X4
Formula 2
R1SiX1X2X3
Formula 3
R1R2SiX1X2
Wherein, R1And R2Each represents hydrogen atom, C independently1-10Alkyl, C3-10Cycloalkyl, C6-15Aryl, C2-30Acryloyl group or contain alkyl, cycloalkyl or the aryl of epoxy radicals; And,
X1, X2, X3, X4Each represents halogen atom or C independently1-5Alkoxyl.
4. according to the composition of claim 1, wherein, organo-metallic compound is to be selected from titanium compound, zirconium compounds, hafnium compounds and aluminium compounds.
5. according to the composition of claim 4; wherein; organo-metallic compound is selected from n-butanol titanium (IV); tert-butyl alcohol titanium (IV); titanium ethanolate (IV); 2-Ethylhexyl Alcohol titanium (IV); isopropyl titanate (IV); (two-isopropoxy) two (pentanedione acid esters) titaniums (IV); two (pentanedione acid esters) titanium oxide (IV); trichlorine three (oxolane) titanium (III); three (2; 2; 6; 6-tetramethyl-3; 5-pimelic acid ester group) titanium (III); (trimethyl) pentamethyl cyclopentadienyltitanium (IV); pentamethyl cyclopentadienyl group titanium trichloride (IV); pentamethyl cyclopentadienyl group trimethoxy titanium (IV); two (cyclohexyl sulfydryl) titaniums (IV) of tetrachloro; two (oxolane) titaniums (IV) of tetrachloro; tetrachloro diamines titanium (IV); four (diethylamino) titanium (IV); four (dimethylamino) titanium (IV); two (tert-butyl group cyclopentadienyl group) titanium chloride; two (cyclopentadienyl group) dicarbapentaborane titanium (II); two (cyclopentadienyl group) titanium chloride; two (ethyl cyclopentadienyl group) titanium chloride; two (pentamethyl cyclopentadienyl group) titanium chloride; two (isopropyl cyclopentadienyl group) titanium chloride; three (2; 2; 6; 6-tetramethyl-3; 5-pimelic acid ester group) oxygen titanium (IV); three isopropoxy chlorine titaniums; the cyclopentadienyl group titanium trichloride; dichloro two (2; 2; 6; 6-tetramethyl-3; 5-pimelic acid ester group) titanium (IV); two (tert-butyl group cyclopentadienyl group) titaniums (IV) of dimethyl; two (isopropoxy) two (2; 2; 6; 6-tetramethyl-3; 5-pimelic acid ester group) titanium (IV); zirconium-n-butylate (IV); zirconium tert-butoxide (IV); ethanol zirconium (IV); zirconium iso-propoxide (IV); zirconium-n-propylate (IV); zirconium acetylacetonate (IV); hexafluoro zirconium acetylacetonate (IV); trifluoroacetyl group pyruvic acid zirconium (IV); four (diethylamino) zirconium; four (dimethylamino) zirconium; four (2; 2; 6; 6-tetramethyl-3; 5-pimelic acid ester group) zirconium (IV); zirconium sulfate (IV) tetrahydrate; n-butanol hafnium (IV); tert-butyl alcohol hafnium (IV); ethanol hafnium (IV); isopropyl alcohol hafnium (IV); isopropyl alcohol one isopropyl acid hafnium (IV); pentanedione acid hafnium (IV); four (dimethylamino) hafnium; Tributyl aluminate; tert-butyl alcohol aluminium (IV); aluminium secondary butylate; aluminium ethylate; aluminium isopropoxide; pentanedione acid aluminium; hexafluoro pentanedione acid aluminium; trifluoroacetyl group pyruvic acid aluminium; and three (2; 2; 6; 6-tetramethyl-3,5-pimelic acid ester group) aluminium.
6. according to the composition of claim 1, wherein, the ratio of organo-metallic compound is 1～300 weight portion based on the hybrid inorganic-organic materials of 100 weight portions.
7. according to the composition of claim 1, wherein, organic polymer is selected from polyester, Merlon, polyvinyl alcohol, polyvinyl butyral, polyacetals, poly-virtueization thing, polyamide, polyamidoimide, Polyetherimide, polyphenylene ether, polyphenylene sulphur, polyether sulfone, polyether-ketone, polyphtalamide, the polyethers nitrile, polyether sulfone, polybenzimidazoles, poly-carbonization imidodicarbonic diamide, polysiloxanes, polymethyl methacrylate, PMAm, nitrile rubber, acrylic rubber, polytetrafluoroethylene, epoxy resin, phenol resin, melamine resin, urea resin, polybutene, polypenthylene, poly-(ethene-copolymerization-propylene), poly-(ethene-copolymerization-butadiene), polybutadiene, polyisoprene, poly-(ethene-copolymerization-propylene diene), butyl rubber, polymethylpentene, polystyrene, poly-(styrene-copolymerization-butadiene), hydrogenation gathers (styrene-copolymerization-butadiene), hydrogenated polyisoprene and hydrogenated butadiene polymer.
8. according to the composition of claim 1, wherein, the ratio of organic polymer is 0.01～50 weight portion based on the hybrid inorganic-organic materials of 100 weight portions.
9. according to the composition of claim 1, wherein, solvent is selected from aliphatic solvent; Aromatic hydrocarbon solvent; Ketones solvent; Ether solvent; The acetate esters solvent; Alcohols solvent; Amide solvent; The silicon kind solvent; And their mixture.
10. according to the composition of claim 1, wherein, the organic solvent content in the composition is 20～99.9 weight %.
11. a method of making organic insulator, comprising:
With the composition coated substrate of claim 1 to form dielectric film; And
Solidify dielectric film.
12. according to the method for claim 11, wherein, with spin-coating method, dip coating, print process, spraying process or rolling method coating dielectric film.
13. according to the method for claim 11, wherein, dielectric film solidified 0.5～2 hour down in 70～150 ℃.
14. organic insulator of making according to the method for claim 11.
15. an OTFT, comprising: base material; Gate electrode; Dielectric film; Organic active layer and source-drain electrode, wherein dielectric film is the organic insulator of claim 14.
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| CN106478952A (en)* | 2015-08-31 | 2017-03-08 | 三星电子株式会社 | Compositionss, electronic device, thin film transistor (TFT) and capacitor |
| CN106478952B (en)* | 2015-08-31 | 2021-06-01 | 三星电子株式会社 | Compositions, electronic devices, thin film transistors, and capacitors |
| CN110072923A (en)* | 2016-11-30 | 2019-07-30 | 瀚森有限责任公司 | Composition for insulating tape |
| WO2018227788A1 (en)* | 2017-06-15 | 2018-12-20 | 北京大学深圳研究生院 | High dielectric constant composite material and application thereof |
| US11322701B2 (en) | 2017-06-15 | 2022-05-03 | Peking University Shenzhen Graduate School | High dielectric constant composite material and application thereof |
| WO2025179615A1 (en)* | 2024-02-26 | 2025-09-04 | 五邑大学 | Hybrid insulating film, and preparation method therefor and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101012950B1 (en) | 2011-02-08 |
| EP1524299A1 (en) | 2005-04-20 |
| KR20050036171A (en) | 2005-04-20 |
| DE602004027980D1 (en) | 2010-08-19 |
| US8017245B2 (en) | 2011-09-13 |
| EP1524299B1 (en) | 2010-07-07 |
| JP4562027B2 (en) | 2010-10-13 |
| US20060147715A1 (en) | 2006-07-06 |
| CN1607685B (en) | 2012-02-29 |
| JP2005120371A (en) | 2005-05-12 |
| US20050259212A1 (en) | 2005-11-24 |
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